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| United States Patent |
5,587,142
|
|
Horwitz
, et al.
|
December 24, 1996
|
Method of dissolving metal oxides with di- or polyphosphonic acid and a
redundant
Abstract
A method of dissolving metal oxides using a mixture of a di- or
polyphosphonic acid and a reductant wherein each is present in a
sufficient amount to provide a synergistic effect with respect to the
dissolution of metal oxides and optionally containing corrosion inhibitors
and pH adjusting agents.
| Inventors:
|
Horwitz; Earl P. (Argonne, IL);
Chiarizia; Renato (Argonne, IL)
|
| Assignee:
|
Arch Development Corporation (Chicago, IL)
|
| Appl. No.:
|
480049 |
| Filed:
|
June 6, 1995 |
| Current U.S. Class: |
423/658.5; 423/10; 423/20; 423/21.1; 423/49; 423/53; 423/150.1 |
| Intern'l Class: |
B01F 001/00; C01G 056/00; C01G 037/00; C01F 017/00 |
| Field of Search: |
423/20,21.1,98,53,49,658.5,150.1,10
|
References Cited
U.S. Patent Documents
| 3933728 | Jan., 1976 | Henbest | 260/37.
|
| 3935125 | Jan., 1976 | Jacob | 252/181.
|
| 3940436 | Feb., 1976 | Kerst | 260/502.
|
| 4082683 | Apr., 1978 | Galesloot | 252/105.
|
| 4132526 | Jan., 1979 | Schwarz et al. | 210/57.
|
| 4293529 | Oct., 1981 | Reese et al. | 423/18.
|
| 4302427 | Nov., 1981 | Berry et al. | 423/10.
|
| 4302429 | Nov., 1981 | Lawes et al. | 299/5.
|
| 4316877 | Feb., 1982 | Tunick et al. | 423/10.
|
| 4460548 | Jul., 1984 | Sturtz | 423/10.
|
| 4464346 | Aug., 1984 | Sturtz et al. | 423/10.
|
| 4499833 | Feb., 1985 | Grantham | 110/342.
|
| 4512900 | Apr., 1985 | Macar et al. | 210/760.
|
| 4554090 | Nov., 1985 | Jones | 252/181.
|
| 4579720 | Apr., 1986 | Budnick | 423/10.
|
| 4656012 | Apr., 1987 | Jdid et al. | 423/10.
|
| 4664811 | May., 1987 | Operhofer | 210/673.
|
| 4747975 | May., 1988 | Ritter | 252/80.
|
| 4802990 | Feb., 1989 | Inskeep, Jr. | 210/701.
|
| 4810405 | Mar., 1989 | Waller et al. | 252/81.
|
| 4937002 | Jun., 1990 | Bainbridge et al. | 252/180.
|
| Foreign Patent Documents |
| 977112 | Mar., 1960 | GB.
| |
Other References
I. H. Warren, "Removal of Iron . . . Minerals", Unit Processes in
Hydrometallurgy, vol. 24, pp. 300-307, Feb. 24-28, 1963.
Database WPI, Derwent Publications, London (GB), 1989, Week 28, An
89-204603 & SU-A-144603 (Ivan Khimprod Ind) Jul. 10, 1989.
|
Primary Examiner: Bos; Steven
Attorney, Agent or Firm: Frishauf, Holtz, Goodman, Langer & Chick, P.C.
Goverment Interests
This invention was developed under contract from the DOE W-31-109-ENG-38.
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of applicaton Ser. No. 08/111,782, filed
Aug. 25, 1993 now abandoned, which is a continuation of application Ser.
No. 07/766,841, filed on Sep. 27, 1991 (abandoned), which is a divisional
of application Ser. No. 07/516,436, filed Apr. 30, 1990 now U.S. Pat. No.
5,078,894, issued Jan. 7, 1992.
This application is related to PCT International Patent Application No.
PCT/US89/04857 which deals with complexing agents for solubilizing certain
heavy metals.
Claims
What is claimed is:
1. A method of dissolving a metal oxide comprising contacting the metal
oxide with a composition comprising a di- or polyphosphonic acid and
sodium formaldehyde sulfoxylate, each being present in sufficient amount
to provide a synergistic effect with respect to the dissolution of the
metal oxide, the composition optionally containing corrosion inhibitors
and pH adjusting agents.
2. The method of claim 1, wherein the metal oxide is an oxide of iron, an
actinide or a lanthanide.
3. The method of claim 1, wherein the metal oxide is an oxide of chromium,
lead or manganese.
4. The method of claim 1, wherein the metal oxide is a surface layer on a
solid substrate.
5. The method of claim 4, wherein the metal oxide is an iron oxide and the
substrate solid substrate is iron or an iron-containing alloy.
6. The method of claim 4, wherein the metal oxide layer contains
radioactive materials and the method is used for decontamination of the
solid substrate by dissolving the metal oxide layer.
7. The method of claim 1, wherein the metal oxide is present in a
particulate substrate, and the contacting comprises washing or leaching
the particulate substrate to remove the metal oxide.
8. The method of claim 7, wherein the metal oxide is an iron oxide, and the
particulate substrate is kaolin or silica.
9. The method of claim 7, wherein the particulate substrate is soil which
contains radioactive contaminants in the form of metal oxides and the
method comprises removing the radioactive contaminants by dissolving them
in said composition.
10. The method of claim 9, wherein contacting of the metal oxide with the
composition comprises heap leaching or in-situ contacting methods.
11. The method of claim 7, wherein the particulate substrate is an ion
exchange resin.
12. The method of claim 1, wherein the metal oxide is in radioactive
nuclear waste sludges and the method comprises partially or completely
dissolving the sludge.
13. The method of claim 1, wherein said composition comprises 0.01M-3M of
the di- or polyphosphonic acid, said mixture having a molar ratio of the
di- or polyphosphonic acid to the reductant of at least 0.5.
14. The method of claim 1, wherein said composition contains said corrosion
inhibitors and/or a sufficient amount of said pH adjusting agent to raise
the pH of the mixture to at least 7.
15. The method of claim 1, wherein the di- or polyphosphonic acid is VDPA,
DHEDPA, methylenedisphosphonic acid or nitrolotris(methylenephosphonic
acid).
16. The method of claim 1, wherein the di- or polyphosphonic acid is HEDPA.
17. The method of claim 1 wherein the metal oxide is iron oxide, chromium
oxide, lead oxide, maganese oxide, an oxide of an actinide and an oxide of
a lanthanide.
18. A method of recovering metal values from metal oxide containing
materials comprising
dissolving the metal oxide by forming a complex with a mixture of a di- or
polyphosphonic acid sodium formaldehyde sulfoxylate, each being present in
a sufficient amount to provide a synergistic effect with respect to the
dissolution of the metal oxide;
releasing the metal oxide from the complex and then recovering the metal
values.
19. The method of claim 18 wherein the metaloxide is iron oxide, chromium
oxide, lead oxide, manganese oxide, an oxide of an actinide and an oxide
of a lanthanide.
20. The method of claim 18, wherein the complex is destroyed by treatment
with an oxidizing agent to release the metal oxides.
21. The method of claim 20, wherein the oxidizing agent is hydrogen
peroxide.
22. The method of claim 18, wherein the mixture further contains a pH
adjusting agent or a corrosion inhibitor.
Description
BACKGROUND OF THE INVENTION
The present invention relates to a synergistic composition for dissolving
metal oxides and in particular iron oxides.
The dissolution of iron oxides is a very important technological process
with applications in a number of different fields. Effective dissolution
agents can be useful for (1) leaching of oxide ores in hydrometallurgy to
recover metal values from the oxide ores; (2) removal of iron oxide
contaminants from non-metallic materials such as minerals (e.g. kaolin and
silica), of importance for the glass and ceramic manufacturing industry;
(3) stripping of metal ions from extraction solvents or from ion exchange
resins; (4) cleaning of metals prior to subsequent processing (e.g.
removal of scale from a metal prior to rolling, anodizing, galvanizing or
painting; (5) removal of deposits from equipment in contact with hot water
or steam (e.g. thermal power equipment, heat exchangers and piping, and
boilers); (6) cleaning or treatment of rusty bolts, nuts and connectors;
(7) removal of stains (iron oxide related) from fabrics; and (8) treatment
of radioactive materials including removal of a surface layer of oxides
from steel equipment used for radioactive material processing or in
nuclear plants, in order to facilitate the removal of radioactive
contaminants (e.g. the actinide and lanthanide elements) present in or
below the surface oxide layers by subsequent application of an appropriate
complexing agent; leaching of radioactive sludge; and leaching of
radioactive soil.
It is known in the art that acids accelerate the dissolution of metal
oxides; however severe conditions of concentration or temperature are
usually required to achieve fast rates. These conditions present safety
hazards in handling and the potential for corrosion, if metals are
present.
It is also known in the art that reductants can accelerate the dissolution
of metal oxides, but the dissolution rates under moderate conditions are
still low.
In general this can be seen in the following:
GB-1229582 ((Albright & Wilson Mfg. Ltd.-1971)- U.S. Pat. No. 3634257
(1972) equivalent) describes the use of phosphonic acids to remove
encrustations containing calcium carbonate or iron compounds from rigid
surfaces, e.g. stills and boiler tubes. The preferred acid is
1-hydroxyethylidene-1,1-diphosphonic acid, which can also be used with
other scale removing acids and with ammonia.
Albright & Wilson sells a product based on GB 1229582, BRIQUEST DP 13, for
use as a railway carriage cleaner. It is described as a blend of BRIQUEST
ADPA (1-hydroxyethylidene-1,1-diphosphonic acid) and orthophosphoric acid
specifically formulated for use with carriage-washing machines.
Valverde N. and Wagner, C., Ber. Bunsenges Physik. Chem. 80(4) (1976) 330
and Valverde N., Ber. Bunsenges. Physik. Chem. 80(4) (1976) 333 describe
experiments which show that the dissolution of iron oxide is accelerated
by decreasing the redox potential and attribute this to reduction of
Fe.sup.+3 in the oxide lattice to give the more soluble Fe.sup.+2.
Lu, Z. Y. and Muir, D. M., Hydrometallurgy 21 (1988) 9 describes
experiments in which an enhanced leaching rate of metal ferrites and iron
oxides is found when HCl leaching solutions also contain Cu.sup.+1 or
Sn.sup.+2 as reductants.
Zinder, B., Furrer, G. and Stomm, W., Geochimica et Cosmochimica Acta 50
(1986) 1861 describes acceleration of the rate of alpha - FeOOH
dissolution by NaNO.sub.3 in the presence of ascorbic acid.
Surana, V. S. and Warren, H. J., Trans. Inst. Min. Metal. Sec. C, 28 (1969)
C133-C139 and Kunda, W., Rudyk, B. and Mackiw, V. N., Bull. Can. Inst.
Min. Metall. 61 (1968) 819 describe the use of SO.sub.2 in dissolution of
iron oxides.
Warren, I. H., "Removal of Iron Oxide from Silicate Minerals" in M. E.
Wadsworth and F. T. Davis (Eds.), Unit Processes in Hydrometallurgy, Vol.
1, pages 300-307, A.I.M.E., New York, 1964 describes the use of sodium
dithionite in dissolution of iron oxides.
Gorichev, I. G. and Kipriyanov, N. A., "Regular Kinetic Features of the
dissolution of Metal Oxides in Acidic Media", Russian Chemical Reviews
53(11) (1984) 1039 is a review article which discusses the effect of redox
couples on the rate of dissolution of metal oxides.
Azuma, K. and Kametani, H., Trans. Metall., Soc. AIME 230 (1964) 853
indicates that the rate of dissolution of iron oxides increases with the
stability constant of Fe.sup.+3 with the anion of the electrolyte.
Banwart, S., Davies, S. and Strumm, W., Colloids and Surfaces 39 (1989)
303, describes the use of oxalic acid and L-ascorbic acid to dissolve iron
oxide and shows an advantage for using the two together.
Gorichev, I. V., Gorsheneva, V. F., Kipriyanov, N. A. and Klyuchnikov, N.
G., Kinetika i Kataliz 21 (6) (1980) 1422, describes the dissolution of
magnetite (Fe.sub.3 O.sub.4) with 1-hydroxyethylidene-1,1-diphosphonic
acid and refers to the potential use in removal of magnetite deposits and
scale from steel.
U.S. Pat. No. 3,854,996 to Frost teaches the use of polyphosphonic acids to
remove magnetite (iron oxide) scale. To help with the action, the use of
an oxidizing agent is recommended.
BRIEF DESCRIPTION OF THE INVENTION
Metal oxides and metal salts are dissolved by treatment with aqueous
solutions containing mixtures of di- or polyphosphonic acids and reducing
agents, preferably sulfur based. Optionally, the solution can contain
corrosion inhibitors and pH adjusting agents.
The mixtures according to the present invention produce dissolution rates
which are substantially higher than those observed with either the acids
or the reductants by themselves.
Of the di- and polyphosphonic acids, 1-hydroxyethylidene-1,1-diphosphonic
acid (HEDPA) is especially preferred for its high activity.
Preferred reductants are the sulfur-based reducing agents such as sodium
sulfite (Na.sub.2 SO.sub.3) and especially sodium formaldehyde sulfoxylate
(SFS) and sodium dithionite (Na.sub.2 S.sub.2 O.sub.4).
When used on some metal surfaces, it is expected that corrosion can be a
problem. Corrosion inhibitors or pH adjustors (to neutralize the normally
acid mixture or render it basic) can reduce corrosion problems.
The inventive mixtures can be used especially to remove radioactive
contaminants from equipment and tools used in handling and processing
radioactive materials and in dissolving radioactive sludge and removing
radioactive oxides and salts from contaminated soil where alternative
methods are not readily available.
DETAILED DESCRIPTION
The invention is based on the discovery that aqueous mixtures of di- or
polyphosphonic acids and reducing agents produce unexpectedly high
dissolution rates as compared with the rates obtained for acids or for
reducing agents alone, or mixtures thereof in general.
Reducing agents include sulfur-based reducing agents such as sulfurous
acid, disulfurous acid, dithionous acid, hydroxymethylsulfinic acid (acid
of SFS), hydroxymethyl sulfonic acid, and their salts; phosphorous based
reductants such as phosphorous acid, hypophosphorous acid and their salts;
aldehyde or hydroxymethyl adducts thereof, such as formaldehyde,
acetaldehyde, hydroxymethylsulfinic acid, hydroxymethyl sulfonic acid, or
their salts, tetrakis(N,N,N',N,-hydroxymethyl)urea, and a
tetrakis(hydroxymethylphosphonium) salt. Nascent hydrogen (produced in
situ) and water soluble salts forming Cr.sup.+2 V.sup.+2 and Cu.sup.+1 are
further examples of reductants for use in the present invention.
The synergistic effect is very pronounced in the case of di- or
polyphosphonic acids mixed with sulfur-based reducing agents, and
especially a combination of HEDPA and SFS. Very high rates were also
observed for hydrogen produced in situ (by reaction of Zn in an acid
media). Both HEDPA and SFS by themselves produce very low dissolution
rates, but when combined, very fast dissolution rates are obtained even at
25 degrees Centigrade. This permits safer, faster and easier processing
while minimizing the risk of corrosion. Corrosion can be further inhibited
using pH adjustors or usual corrosion inhibitors.
For an acidic mixture as described above, a pH adjustor will normally be a
basic substance. Thus, when pH adjustors are used, the acids will be at
least partially converted to their salts. pH adjustors are, for example,
alkali metal or alkaline earth metal hydroxides such as sodium, calcium or
potassium hydroxide. As the mixture is neutralized, most or all of the
phosphonic acid will convert into the corresponding alkali metal or
alkaline earth metal salt. This conversion will be substantially complete
when the inventive mixture is adjusted into the alkaline pH range.
Other pH adjusting agents that can be used to advantage include ammonium
and various derivatives thereof e.g. alkyl, alkylene or alkanol
derivatives. Examples of alkyl derivatives include a C.sub.1 -C.sub.3
alkyl amine and especially methyl amine, di- or tri-methyl amine. Alkylene
derivatives include ethylene diamine and others corresponding to the alkyl
compounds. Corresponding alkanol derivatives can also be used, including
diethanoiamine for example.
One important use for this technology is in decontaminating tools, reactors
and other equipment, which have been contaminated with radioactive
materials (e.g. oxides and salts of actinide and lanthanide elements) in
nuclear weapons and nuclear power operations. Although the invention can
be applied quite widely for removal or dissolution of metal oxides as
noted above; for decontamination of radioactive metal surfaces there are
few practical alternatives available. Control of corrosiveness as by pH
adjusting agents or corrosion inhibitors may be particularly important in
these uses, to avoid degrading difficult to replace parts and apparatus.
In order to decontaminate a metal surface according to the invention, the
surface oxide coating containing the radioactive contaminants is removed.
The best way to do this is to attack and dissolve the surface oxide
coating directly. The surface oxide will in most cases be an iron oxide
since most equipment is constructed from iron or iron-containing alloys.
The radioactive contaminants may then be carried or washed into solution
with the iron oxide, or complexed with reactants to take them into
solutions.
A further advantageous use for this technology is for the retrieval and
treatment of high level nuclear waste, at present stored in single or
double shell tanks at a number of nuclear sites. Many of these nuclear
waste solutions have been neutralized in the tanks by addition of alkali,
to reduce their corrosive power. This treatment has generated large
amounts of radioactive sludge in the tanks. In order to retrieve and
further process these wastes to concentrate the high level radioactive
components and carry out permanent disposal, it will be necessary to leach
and/or dissolve the sludge solids to release the radioactive metals into
solutes.
A third use is in the leaching of radioactive or other metal (e.g.
chromium) contaminants from contaminated soils. Leaching of soils is
accomplished by heap leaching or by processing in tanks.
Lead or manganese oxides can be dissolved by contacting with the
composition of this invention.
Another use is for recovering of metal values from metal oxide containing
materials by first dissolving metal oxides by forming a complex with a
mixture of a di- or polyphosphonic acid and a reductant, each being
present in a sufficient amount to provide a synergistic effect with
respect to the dissolution of metal oxides; and thereafter, releasing the
metal oxides from the complex, for recovering or disposal. Releasing the
metal oxide is accomplished by destroying the complex such as by treatment
with an oxidizing agent. A useful oxidizing agent is hydrogen peroxide.
The mixture for dissolving the metal oxide can further contain a pH
adjusting agent or a corrosion inhibitor.
Other uses include treating of oxide ors (as by heap leaching or in tanks)
in hydrometallurgy to leach metal values from the oxide ores; removal of
iron oxide contaminants from non-metallic materials such as minerals (e.g.
kaolin and silica by batch processing in tanks); washing metals with the
inventive composition prior to processing (e.g. removal of scale from a
metal prior to rolling, anodizing, galvanizing or painting); (7) flushing
of pipes, boilers, and etc. for the removal of deposits from surfaces in
contact with hot water or steam by pumping the mixture through the pipes;
cleaning or treatment of rusty bolts, nuts and connectors; and (9) removal
of stains (iron oxide related) from fabrics by solubilizing the iron oxide
and washing it away.
To illustrate the very effective oxide dissolving effectiveness of the
acid/reductant mixtures of the invention, a synthetic iron oxide mineral,
Goethite (alpha-FeOOH), is used as a model.
Experimental procedure
Radioactive synthetic Goethite samples, containing .sup.59 Fe at a level of
1.7.times.10.sup.4 count per minute/mg of dried solid were prepared and
used for this and subsequent dissolution experiments.
The dissolution experiments were performed by contacting in screw-cap glass
tubes a weighed amount of radioactive Goethite (about 50 mg) with the
dissolving medium at a volume-weight ratio of 40 (2 ml for 50 mg). The
size of the particles of iron oxide were estimated to be in the range of
60-120 mesh. The glass tubes containing the Goethite were thermally
equilibrated in a heating bath and then the dissolving solution was added.
The mixture in the glass tubes was agitated using a magnetic stirrer, to
suspend the iron oxide in the dissolving medium. At various time intervals
tubes were withdrawn from the bath; rapidly quenched by cooling; and
thereafter centrifuged to remove the particles of Goethite for suspension.
The iron levels in the supernatant solutions were measured by measuring the
radioactivity of the supernatant solution with a gamma counter. First
order rate constants and induction times for dissolution of the Goethite
were calculated from the measurements by standard methods.
EXAMPLE 1
Samples of the Goethite were treated at 25 degrees Centigrade with 0.1M
solutions of each of the following reductants: hydroquinone, NH.sub.2 OH
HCl, SnCl.sub.2, Na.sub.2 SO.sub.3, Zn(H.sub.2), Na.sub.2 S.sub.2 O.sub.4
and sodium formaldehyde sulfoxylate (SFS), or 1.0M samples of each of the
following diphosphonic acids: 1-hydroxyethylidene-1,1-diphosphonic acid
(HEDPA), vinylidene-1,1-diphosphonic acid (VDPA) and
1,2-dihydroxyethylidene-1,1-diphosphonic acid (DHEDPA).
It is noted that Zn(H.sub.2) indicates the use of hydrogen formed in situ
by use of Zn in an acid medium. It is the nascent hydrogen that acts as
the reductant.
No significant dissolution was observed for any of these reductants. The
first order rate constants were <1.0.times.10.sup.-6 sec.sup.-1. Thus, the
reductants alone and the acids alone are not effective dissolution agents.
EXAMPLE 2
Goethite samples were treated at 25.degree. C. with mixtures of 1M HEDPA
and various reductant using the procedures described in Example 1. The
first order rate constants (k) and induction times (ti) for dissolution of
the solid were measured. The results were as follows:
______________________________________
Reductant k(sec-1) ti(min)
______________________________________
none <1.0 .times. 10.sup.-6
not determined
0.1M hydroquinone
1.0 .times. 10.sup.-6
0
0.1M NH.sub.2 OH'HCl
1.0 .times. 10.sup.-6
0
0.1M SnCl.sub.2
2.3 .times. 10.sup.-5
0
0.1M Na.sub.2 SO.sub.3
2.2 .times. 10.sup.-4
47
0.2M Zn(H.sub.2)
5.0 .times. 10.sup.-4
23
0.1M Na.sub.2 S.sub.2 O.sub.4
1.9 .times. 10.sup.-3
0
0.1M SFS 2.3 .times. 10.sup.-3
8
______________________________________
Although all HEDPA/reductant mixtures provided rate accelerations relative
to the individual components, the accelerations with HEDPA/sodium
dithionite (Na.sub.2 S.sub.2 O.sub.4) and HEDPA/sodium formaldehyde
sulfoxylate (SFS) mixtures were amazingly large (>2000 fold) as compared
with the individual component.
EXAMPLE 3
Goethite samples were treated at 25 degrees Centigrade with 0.1M solutions
of SFS and various diphosphonic acids, using the procedures described in
Example 1. The first order rate constants and induction times for
dissolution of the solid were measured. The results were as follows:
______________________________________
Acid k(sec-1) ti(min)
______________________________________
none <1.0 .times. 10.sup.-6
not determined
HEDPA 2.3 .times. 10.sup.-3
8
VDPA 2.5 .times. 10.sup.-4
0
DHEDPA 3.4 .times. 10.sup.-4
0
______________________________________
All diphosphonic acids gave large (2-3 orders of magnitude) rate
accelerations, with the HEDPA/SFS rate being the largest.
EXAMPLE 4
Goethite samples were treated at 25 degrees Centigrade with various acids
in the presence and absence of 0.1M SFS, using the procedures described in
Example 1. The first order rate constants and induction times for
dissolution of the solid were measured. The results were as follows:
______________________________________
Acid/Reductant k(sec-1) ti(min)
______________________________________
2M HCl/none 2 .times. 10.sup.-6
0
2M HCl/SFS 2.0 .times. 10.sup.-5
0
1M Oxalic/none 5.0 .times. 10.sup.-5
49
1M Oxalic/SFS 5.2 .times. 10.sup.-4
0
______________________________________
Rate accelerations of only about 10 fold were observed with these acids
using SFS as the reductant.
EXAMPLE 5
Goethite samples were treated at 80 degrees Centigrade with various acids
in the presence and absence of 0.1M SFS, using the procedures described in
Example 1. The first order rate constants and induction times for
dissolution of the solid were measured. The results were as follows:
______________________________________
Acid/Reductant k(sec-1) ti(min)
______________________________________
1M HNO.sub.3 /none
4.8 .times. 10.sup.-6
0
1M HNO.sub.3 /SFS 4.1 .times. 10.sup.-5
0
3M H.sub.2 SO.sub.4 /none
5.7 .times. 10.sup.-4
29
3M H.sub.2 SO.sub.4 /SFS
1.9 .times. 10.sup.-3
0
1M HEDPA/none 1.8 .times. 10.sup.-4
120
1M HEDPA/SFS 1.1 .times. 10.sup.-2
0
______________________________________
When combined with mineral acids, rate accelerations of less than an order
of magnitude were observed: SFS gave rate accelerations of 8.5 with 1M
HNO.sub.3 and 3.3 with 3M H.sub.2 SO.sub.4. The rate acceleration with 1M
HEDPA under these conditions was about two orders of magnitude at 78.
EXAMPLE 6
Goethite samples were treated under mild temperature conditions of 25
degrees Centigrade with 1M HEDPA and 0.1M solutions of various reducing
agents, using the procedures described in Example 1. The times for
dissolution of the Goethite were measured and the times in minutes for
dissolution of 10%, 50% and 90% of the solids were calculated. The results
were as follows:
______________________________________
Reductant 10% (min) 50% (min) 90% (min)
______________________________________
NH.sub.2 OH
>100 >100 >100
NH.sub.2 NH.sub.2
>100 >100 >100
Hydroquinone
>100 >100 >100
ascorbic acid
>100 >100 >100
Sn.sup.+2 >100 >100 >100
Na.sub.2 SO.sub.3
42 >100 >100
Zn (H.sub.2)
19 46 >100
SFS 5 13 27
Na.sub.2 S.sub.2 O.sub.4
1 6 27
______________________________________
The particularly high activity available with sulfur based reductants and
in situ formed hydrogen (nascent) can be seen from these results.
EXAMPLE 7
Goethite samples were treated at 80 degrees Centigrade with 0.1M HEDPA and
0.1 M solutions of various reducing agents, using the procedures described
in Example 1. The times for dissolution of the Goethite were measured and
the times in minutes for dissolution of 10%, 50% and 90% of the solids
were calculated. The results were as follows:
______________________________________
Reductant 10% (min) 50% (min) 90% (min)
______________________________________
NH.sub.2 OH
>35 >35 >35
NH.sub.2 NH.sub.2
>35 >35 >35
hydroquinone
14 >35 >35
Sn.sup.+2 3 12 32
ascorbic acid
1 3 9
Zn (H.sub.2)
<1 2 6
Na.sub.2 SO.sub.3
<1 2 5
SFS <1 <1 3
Na.sub.2 S.sub.2 O.sub.4
<1 <1 3
______________________________________
Although treatment under high temperature conditions as compared with
Example 6, resulted in higher activities for all reactants, the
surprisingly more active reductants in accordance with the condition of
Example 6, maintained their comparatively higher activity under the more
rigorous conditions of Example 7.
EXAMPLE 8
The ability to decontaminate metal substrates bearing radioactive
contaminants is shown by the following:
Sample Preparation
Stainless steel discs, approximately one inch in diameter, were
contaminated with .sup.233 U, .sup.239 Pu or .sup.241 Am (actinide series
elements).
Each sample was prepared by 1) oxidizing the surface with hydrogen
peroxide; 2) heating a disc to a dull red heat for a few seconds in air;
3) depositing tracer level concentrations of one of the three actinides,
as a nitrate salt, on the surface of the disc; and 4) heating the disc
again to a dull heat for 10 seconds to insure that the actinide nitrate is
converted to its oxide and to insure that the activity is driven into the
oxide film on the surface of the steel discs.
The sample discs were then counted radiometrically using an internal
proportional alpha counter to measure the quantity of activity on each
disc. These samples represent an extreme case with respect to difficulty
in removing contamination.
Decontamination Testing
The discs were introduced into solutions of
1-hydroxyethylidene-1,1-diphosphonic acid (HEDPA) and SFS as shown in the
following Table. The solutions were stirred with a magnetic stirrer. After
the indicated predetermined period of time, the discs were rinsed with
water, dried on a hot plate and recounted in the proportional alpha
counter. The discs were then leached a second, and in some cases a third
time, using the same procedure. Two series of experiments were performed,
one at room temperature and the other at 70-80 degrees Centigrade. The
results are tabulated below:
______________________________________
Leaching Solution: 1M HEDPA/0.1M SFS
Room Temperature (about 25 degrees Centigrade)
Activity on Disc (Counts/Minute)
Contact Time
233.sub.U 237.sub.Pu 241.sub.Am
______________________________________
none 1.7 .times. 10.sup.+3
1.0 .times. 10.sup.+5
1.0 .times. 10.sup.+5
10 minutes 1.2 .times. 10.sup.+3
3.7 .times. 10.sup.+4
3.9 .times. 10.sup.+4
20 minutes 1.1 .times. 10.sup.+3
2.6 .times. 10.sup.+4
3.8 .times. 10.sup.+4
15 hours 6.9 .times. 10.sup.+2
2.6 .times. 10.sup.+4
8.3 .times. 10.sup.+2
Total % removal
90 74 99
______________________________________
______________________________________
Leaching Solution: 1M HEDPA/0.1M SFS
70-80 degrees Centigrade
Activity on Disc (Counts/Minute)
Contact Time
233.sub.U 237.sub.Pu 241.sub.Am
______________________________________
none 7.3 .times. 10.sup.+3
1.2 .times. 10.sup.+5
1.0 .times. 10.sup.+5
10 minutes 2.1 .times. 10.sup.+2
1.0 .times. 10.sup.+4
2.5 .times. 10.sup.+4
20 minutes 8 9.4 .times. 10.sup.+3
1.8 .times. 10.sup.+4
Total % removal
99.9 92 82
______________________________________
Discussion
Although there is an additive effect for dissolution of metal oxides when
combining various acids with reductants, a synergistic effect is shown
when di- and polyphosphonic acids are used. This includes the
aminophosphonic acids such as aminotris(methylenephosphonic acid). The
reductants include organic reductants, such as ascorbic acid and
hydroquinone and inorganic reductants. Sulfur-based reductant such as
sodium sulfite, sodium dithionite and sodium formaldehyde sulfoxylate show
the greatest effect. Hydrogen formed in situ shows a similar strong
effect.
Acid concentrations can range up to the concentration of standard
concentrated acid as manufactured, but are preferably in the 0.01-3M
range. The reductant concentrations can range up to about 5M, but are
preferably in the 0.001-0.3M range. The ratio of acid to reductant is
preferably at least 0.5, more preferably at least 5 and most preferably at
least 10.
The treatment temperatures can range from ambient up to the reflux
temperature of the treatment solution., but preferably in the ambient to
80 degrees Centigrade range. Treatment at ambient temperature is
especially preferred.
Methods of Use
To use the inventive composition for decontaminating hand tools or other
small pieces of equipment which may have been contaminated such as by use
in a nuclear power plant, it is possible simply to dip the equipment or
tools into a container of a composition in accordance with the present
invention. Alternatively, the composition can be sprayed onto the surface
or rubbed on with a suitable applicator.
Depending on the amount of contamination and the condition of the
equipment, a contact time of several minutes should be used. A contact
time of 10 minutes up to about 1 hour is preferable. This can be
determined by measuring the residual radiation of the tools to be sure
that they are properly decontaminated. As shown in Example 8 above, even
with baked-in contaminants, substantial reduction in contamination is
possible after 1 hour although some samples were treated for up to 24
hours.
If it is desired to decontaminate pipes through which radioactive fluids
have passed, or just to remove iron oxides from the inside of the pipes
through which water or steam has passed, essentially the same principle
apples. A composition in accordance with the present invention is
circulated through the pipes or other equipment to be decontaminated for a
sufficient time to accomplish the required results. Spraying or applying
with a suitable applicator may also be used. If equipment is being
decontaminated, the level of radiation can be measured to determine when
the treatment is sufficient. The removal of scale or other iron oxide
deposits can be determined by inspection or, in extreme cases where there
is clogging, by a reduction in the back pressure on the materials being
pumped through the system.
Removal of iron oxide contaminants can be done using usual equipment to
leach contaminants from many types of materials. Heap leaching of soil or
ore can be practiced, for example.
The treatment of radioactive sludge can also be accomplished by leaching
the sludge with the inventive materials although usual precautions
necessary for handling such materials must be applied. Leaching can be
accomplished by heap-leaching or batch processing methods such as are
usual in metal value recovery operations used in the mining industry.
The above is by way of illustration of preferred embodiments of the
invention but is not considered limitative of the scope of the invention
which is defined by the following claims.
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